CN107394268B - Lithium secondary cell electrolyte and its lithium secondary battery - Google Patents

Lithium secondary cell electrolyte and its lithium secondary battery Download PDF

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Publication number
CN107394268B
CN107394268B CN201710629568.3A CN201710629568A CN107394268B CN 107394268 B CN107394268 B CN 107394268B CN 201710629568 A CN201710629568 A CN 201710629568A CN 107394268 B CN107394268 B CN 107394268B
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lithium secondary
secondary cell
electrolyte
cell electrolyte
propyl
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CN107394268A (en
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范伟贞
余乐
廖波
周邵云
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Guangzhou Tinci Materials Technology Co Ltd
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Guangzhou Tinci Materials Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a kind of lithium secondary cell electrolyte and its lithium secondary batteries, lithium secondary cell electrolyte includes organic solvent, electric conducting lithium salt and additive, the additive is nitrogenous silicon oxide compound, and the nitrogenous silicon oxide compound has such as following formula I structure: where R1, R2, R3, R4, R5, R6, R7Separately it is selected from methyl or ethyl；0≤a≤1.Above-mentioned electrolyte can be such that the content of the HF in electrolyte reduces, reduce corrosion of the HF to positive electrode, improve the thermal stability of electrolyte by adding nitrogenous silicon oxide compound；Improve the cycle performance of electrolyte under high pressure, improve the service life of lithium secondary battery, while battery high-temperature can be inhibited to store flatulence.

Description

Lithium secondary cell electrolyte and its lithium secondary battery
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of lithium secondary cell electrolyte and its contain this The lithium secondary battery of electrolyte.
Background technique
In existing commercialization secondary cell, lithium secondary battery is since specific energy is high, operating voltage is high, operating temperature model Wide and good cycle is enclosed, is widely used in military and civilian compact electric apparatus, such as mobile phone, portable computer, takes the photograph Shadow machine, or even it is used for electric car and hybrid-electric car.However, with the fast development of electronic product and electric car, it is right More stringent requirements are proposed for the cruising ability of lithium secondary battery.In order to provide the energy density of higher lithium secondary battery, one Effective mode is to improve the voltage of lithium secondary battery.
But under high pressure, the various transition metal elements in positive electrode material of lithium secondary cell are in higher oxidation state, On the one hand oxidation activity with higher makes electrolyte easily aoxidize in side of the positive electrode and generate a large amount of gaseous matter, in turn Lead to battery flatulence；On the other hand, the transition metal of high price oxidation state is due to lesser ionic radius, easily from it is positive this It is dissolved out in body phase, is electrolysed the solid electrolyte interface protective film that liquid phase deposits to negative side and destroys negative terminal surface and (is commonly called as SEI Film), and then lead to battery capacity sharp-decay.At high temperature, with LiPF6For lithium secondary battery of electrolyte electrolyte, due to The presence of trace water, which is easy to decompose, produces a variety of Bronsted acids (such as HF) and lewis acid (such as PF5), to accelerate catalysis electricity Solve the oxygenolysis of liquid ingredient and the dissolution migration of transition metal element.
Therefore, the electricity for making lithium ion battery keep excellent cycle performance is remained under high voltages it is necessory to develop one kind Solve liquid.
Summary of the invention
Based on this, the object of the present invention is to provide a kind of lithium secondary cell electrolytes.
Specific technical solution is as follows:
A kind of lithium secondary cell electrolyte, including organic solvent, electric conducting lithium salt and additive, the additive are nitrogenous Silicon oxide compound, the nitrogenous silicon oxide compound have such as following formula I structure:
Wherein, R1, R2, R3, R4, R5, R6, R7Separately it is selected from methyl or ethyl；0≤a≤1.
In wherein some embodiments, the nitrogenous silicon oxide compound is selected from bis- (3- (trimethoxy silane base) propyl) It is amine (1), bis- (3- (triethoxysilicane alkyl) propyl) amine (2), bis- (3- (trimethoxy silane base) propyl)-N- methylamines (3), double In (3- (trimethoxy silane base) propyl) ethylenediamine (4) or bis- (3- (triethoxysilicane alkyl) propyl) ethylenediamine (5) extremely Few one kind.Structural formula is as follows:
In wherein some embodiments, the dosage of the nitrogenous silicon oxide compound accounts for lithium secondary cell electrolyte gross mass 0.01-10.00%.
In wherein some embodiments, the electric conducting lithium salt is at least one in lithium hexafluoro phosphate or double fluorine sulfimide lithiums Kind；The electric conducting lithium salt accounts for the 8.00-16.00% of lithium secondary cell electrolyte gross mass.
In wherein some embodiments, the organic solvent is made of cyclic solvent and linear solvents, the cyclic solvent Mass ratio with the linear solvents is (1~2): 3.
The dosage of the organic solvent accounts for the 74.00-91.99% of lithium secondary cell electrolyte gross mass
In wherein some embodiments, the cyclic solvent is selected from ethylene carbonate, propene carbonate, fluoro ethylene carbonate One or more of ester, gamma-butyrolacton and gamma-valerolactone.
In wherein some embodiments, the linear solvents be selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, One or more of ethyl acetate, methyl propyl carbonate, propyl propionate.
It is a further object of the present invention to provide a kind of lithium secondary batteries.
A kind of lithium secondary battery, comprising above-mentioned lithium secondary cell electrolyte, (positive plate also containing a positive electrode active material contains There are the negative electrode tab and diaphragm of negative electrode active material).
The positive electrode active materials described in above-mentioned lithium secondary battery refer to lithium-containing transition metal compound, the mistake containing lithium Crossing metallic compound is Li1+a(NixCoyM1-x-y)O2、Li(NipMnqCo2-p-q)O4、LiMh(PO4)mAt least one, wherein 0≤ A≤0.3,0≤x≤1,0≤y≤1, the 0 < < of x+y≤1,0≤p≤2,0≤q≤2,0 p+q≤2, M Fe, Ni, Co, Mn, Al Or 5,0 < m < 5 of V, 0 < h <；The negative electrode active material includes lithium metal, lithium alloy, carbon material, silica-base material and tinbase material At least one of material.
Above-mentioned lithium secondary cell electrolyte have the following advantages that and the utility model has the advantages that
(1) above-mentioned electrolyte can be such that the content of the HF in electrolyte reduces, subtract by adding nitrogenous silicon oxide compound Few corrosion of the HF to positive electrode, improves the thermal stability of electrolyte；
(2) above-mentioned electrolyte improves the cycle performance of electrolyte under high pressure, mentions by adding nitrogenous silicon oxide compound The service life of high lithium secondary battery, while battery high-temperature can be inhibited to store flatulence.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases Any and all combinations of the listed item of pass.
Embodiment 1
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 91.99% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 8.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl) amine, dosage 0.01%.It will The electrolyte of the present embodiment is used for LiNi0.6Co0.2Mn0.2O2/ graphite soft-package battery.
Embodiment 2
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 85.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 12.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl) amine, dosage 3.00%. By the electrolyte LiNi of the present embodiment0.5Co0.2Mn0.3O2/ graphite soft-package battery.
Embodiment 3
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 82.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester, dimethyl carbonate) composition, the mass ratio of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate is 1:1:1.Described six Lithium fluophosphate accounts for the 8.00% of lithium secondary cell electrolyte gross mass.The electrolysis additive is bis- (3- (trimethoxy silanes Base) propyl) amine, dosage 10.00%.By the electrolyte LiNi of the present embodiment0.8Co0.15Al0.05O2/ graphite soft-package battery.
Embodiment 4
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 91.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester, diethyl carbonate) composition, the mass ratio of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is 1:1:1.Described six Lithium fluophosphate accounts for the 8.00% of lithium secondary cell electrolyte gross mass.The electrolysis additive is bis- (3- (triethoxysilanes Base) propyl) amine, dosage 1.00%.By the electrolyte LiNi of the present embodiment0.5Co0.2Mn0.3O2The compound soft-package battery of/silicon-carbon.
Embodiment 5
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 85.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester and diethyl carbonate) composition, the mass ratio of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is 3:5:2.Described six Lithium fluophosphate accounts for the 12.00% of lithium secondary cell electrolyte gross mass.The electrolysis additive is bis- (3- (triethoxysilicanes Alkyl) propyl) amine, dosage 3.00%.By the electrolyte LiNi of the present embodiment0.6Co0.2Mn0.2O2/ graphite soft-package battery.
Embodiment 6
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 81.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester and diethyl carbonate) composition, the mass ratio of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate is 3:5:2.Described six Lithium fluophosphate accounts for the 14.00% of lithium secondary cell electrolyte gross mass.The electrolysis additive is bis- (3- (triethoxysilicanes Alkyl) propyl) amine, dosage 5.00%.By the electrolyte LiNi of the present embodiment0.5Co0.2Mn0.3O2/ graphite soft-package battery.
Embodiment 7
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 84.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 16.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl)-N- methylamines, dosage 2.00%.By the electrolyte LiCoO of the present embodiment2/ graphite soft-package battery.
Embodiment 8
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 85.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 12.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl)-N- methylamines, dosage 3.00%.By the electrolyte LiCoO of the present embodiment2/ graphite soft-package battery.
Embodiment 9
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 74.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 16.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl)-N- methylamines, dosage 10.00%.By the electrolyte LiNi of the present embodiment1/3Co1/3Mn1/3O2/ graphite soft-package battery.
Embodiment 10
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 83.99% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 16.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl) ethylenediamines, dosage 0.01%.By the electrolyte LiCoO of the present embodiment2/ graphite soft-package battery.
Embodiment 11
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 87.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 8.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl) ethylenediamines, dosage 5.00%.By the electrolyte LiCoO of the present embodiment2/ graphite soft-package battery.
Embodiment 12
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 82.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 12.00% of liquid gross mass.The electrolysis additive is bis- (3- (trimethoxy silane base) propyl) ethylenediamines, dosage 6.00%.By the electrolyte LiNi of the present embodiment0.8Co0.1Mn0.1O2/ graphite soft-package battery.
Embodiment 13
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 91.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 8.00% of liquid gross mass.The electrolysis additive is bis- (3- (triethoxysilicane alkyl) propyl) ethylenediamines, dosage 1.00%.By the electrolyte LiNi of the present embodiment0.3Co0.3Mn0.3O2/ graphite soft-package battery.
Embodiment 14
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 89.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 8.00% of liquid gross mass.The electrolysis additive is bis- (3- (triethoxysilicane alkyl) propyl) ethylenediamines, dosage 3.00%.By the electrolyte LiNi of the present embodiment0.6Co0.2Mn0.2O2/ graphite soft-package battery.
Embodiment 15
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 83.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The lithium hexafluoro phosphate accounts for lithium secondary battery electrolysis The 12.00% of liquid gross mass.The electrolysis additive is bis- (3- (triethoxysilicane alkyl) propyl) ethylenediamines, dosage 5.00%.By the electrolyte LiNi of the present embodiment0.8Co0.1Mn0.1O2/ graphite soft-package battery.
Embodiment 16
A kind of lithium secondary cell electrolyte of the present embodiment, is made of organic solvent, electric conducting lithium salt and additive.It is described organic Solvent accounts for the 89.00% of lithium secondary cell electrolyte gross mass, by cyclic solvent (ethylene carbonate) and linear solvents (carbonic acid first Ethyl ester) it forms, the mass ratio of ethylene carbonate and methyl ethyl carbonate is 1:2.The electric conducting lithium salt is double fluorine sulfimide lithiums, is accounted for The 9.00% of lithium secondary cell electrolyte gross mass.The electrolysis additive is bis- (3- (triethoxysilicane alkyl) propyl) second Diamines, dosage 2.00%.By the electrolyte LiNi of the present embodiment0.6Co0.2Mn0.2O2/ graphite soft-package battery.
Comparative example 1
The preparation method of the electrolyte of this comparative example is same as Example 1, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl) amine compounds, this electrolyte is applied in the same manner as shown in Example 1 to test its property in battery Energy.
Comparative example 2
The preparation method of the electrolyte of this comparative example is same as Example 2, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl) amine compounds, this electrolyte is applied to test its property in battery according to method same as Example 2 Energy.
Comparative example 3
The preparation method of the electrolyte of this comparative example is same as Example 3, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl) amine compounds, this electrolyte is applied to test its property in battery according to method same as Example 3 Energy.
Comparative example 4
The preparation method of the electrolyte of this comparative example is same as Example 4, the difference is that not using bis- (3- (three ethoxies Base silane base) propyl) amine compounds, this electrolyte is applied to test its property in battery according to method same as Example 4 Energy.
Comparative example 5
The preparation method of the electrolyte of this comparative example is same as Example 5, the difference is that not using bis- (3- (three ethoxies Base silane base) propyl) amine compounds, this electrolyte is applied to test its property in battery according to method same as Example 5 Energy.
Comparative example 6
The preparation method of the electrolyte of this comparative example is same as Example 6, the difference is that not using bis- (3- (three ethoxies Base silane base) propyl) amine compounds, this electrolyte is applied to test its property in battery according to method same as Example 6 Energy.
Comparative example 7
The preparation method of the electrolyte of this comparative example is same as Example 7, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl)-N- methylamine compound, this electrolyte is applied to test in battery according to method same as Example 7 Its performance.
Comparative example 8
The preparation method of the electrolyte of this comparative example is same as Example 8, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl)-N- methylamine compound, this electrolyte is applied to test in battery according to method same as Example 8 Its performance.
Comparative example 9
The preparation method of the electrolyte of this comparative example is same as Example 9, the difference is that not using bis- (3- (trimethoxies Base silane base) propyl)-N- methylamine compound, this electrolyte is applied to test in battery according to method same as Example 9 Its performance.
Comparative example 10
The preparation method of the electrolyte of this comparative example is same as in Example 10, the difference is that not using bis- (3- (front threes Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method same as in Example 10 Try its performance.
Comparative example 11
The preparation method of the electrolyte of this comparative example is identical as embodiment 11, the difference is that not using bis- (3- (front threes Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 11 Try its performance.
Comparative example 12
The preparation method of the electrolyte of this comparative example is identical as embodiment 12, the difference is that not using bis- (3- (front threes Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 12 Try its performance.
Comparative example 13
The preparation method of the electrolyte of this comparative example is identical as embodiment 13, the difference is that not using bis- (3- (three second Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 13 Try its performance.
Comparative example 14
The preparation method of the electrolyte of this comparative example is identical as embodiment 14, the difference is that not using bis- (3- (three second Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 14 Try its performance.
Comparative example 15
The preparation method of the electrolyte of this comparative example is identical as embodiment 15, the difference is that not using bis- (3- (three second Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 15 Try its performance.
Comparative example 16
The preparation method of the electrolyte of this comparative example is identical as embodiment 16, the difference is that not using bis- (3- (three second Oxysilane base) propyl) ethylene diamine compound, this electrolyte is applied to survey in battery according to method identical with embodiment 16 Try its performance.
The application experiment of embodiment and comparative example:
Electrolyte stores acidity test: lithium secondary battery prepared by above-described embodiment 1~16 and comparative example 1~16 is electrolysed Liquid is respectively pivoted to seal in Aluminum Bottle, and Aluminum Bottle vacuumizes encapsulation with aluminum plastic film, while being placed in the insulating box that set temperature is 55 DEG C Storage, respectively before storage, storage 2 days, 4 days, 6 days after sampling and testing electrolyte acidity.Acidity test uses potentiometric titration, In terms of HF, acidity unit is ppm, and testing result is as shown in table 1.
Charge-discharge test condition: in order to measure the battery charge and discharge performance using electrolyte produced by the present invention, carry out with Lower operation: conventionally preparing positive/negative plate, and electrolyte fluid injection in glove box is prepared using each embodiment and uses Above-mentioned pole piece prepares 053048 type soft-package battery, with new prestige (BS-9300R type) battery test system to the 053048 type electricity of preparation Pond carries out charge-discharge test, while being compared with the battery of corresponding comparative example electrolyte preparation.Battery is placed in room temperature with 3.0 Charge and discharge cycles are stored with 55 DEG C of full electricity are placed under~4.4V 1C multiplying power.Expansion rate calculation is following formula:
Wherein, T is the cell thickness after high temperature storage, T0For the cell thickness before high temperature storage.Lithium secondary battery test Partial results are referring to table 2.
Before the electrolyte high temperature storage of 1 embodiment and comparative example of table, 3 days and acidity test result after 6 days:
Test result after the charge and discharge cycles and high temperature storage of 2 embodiment and comparative example of table:
As can be seen from Table 1: embodiment 1~16 adds appointing in the present invention into electrolyte relative to comparative example 1~16 The nitrogenous silicon oxide compound of one kind of anticipating can significantly inhibit acidity of electrolyte during 55 DEG C of ambient storages and rise, bright The aobvious thermal stability for improving electrolyte
As can be seen from Table 2, additive is to the full electricity storage of the capacity retention ratio and high temperature of lithium secondary battery normal temperature circulation Expansion rate has apparent advantageous effects, and the present invention is added in electrolyte using nitrogenous silicon oxide compound with outstanding excellent Gesture is mainly manifested in the circulation volume conservation rate for promoting battery and reduces the cell expansion rate of full electricity storage under high temperature.Embodiment 1-16 is substantially better than its comparative example.
Therefore the battery of application electrolyte of the present invention has high security performance and durability, has high market Value and social benefit.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.

Claims (8)

1. a kind of lithium secondary cell electrolyte, which is characterized in that including organic solvent, electric conducting lithium salt and additive, the addition Agent is nitrogenous silicon oxide compound, and the nitrogenous silicon oxide compound has such as following formula I structure:
Wherein, R1, R2, R3, R4, R5, R6, R7Separately it is selected from methyl or ethyl；0≤a≤1.
2. lithium secondary cell electrolyte according to claim 1, which is characterized in that the nitrogenous silicon oxide compound is selected from Bis- (3- (trimethoxy silane base) propyl) amine, bis- (3- (triethoxysilicane alkyl) propyl) amine, bis- (3- (trimethoxy silanes Base) propyl)-N- methylamine, bis- (3- (trimethoxy silane base) propyl) ethylenediamines or bis- (3- (triethoxysilicane alkyl) propyl) At least one of ethylenediamine.
3. lithium secondary cell electrolyte according to claim 1 or 2, which is characterized in that the nitrogenous silicon oxide compound Dosage account for the 0.01-10.00% of lithium secondary cell electrolyte gross mass.
4. lithium secondary cell electrolyte according to claim 1 or 2, which is characterized in that the electric conducting lithium salt is hexafluoro phosphorus At least one of sour lithium or double fluorine sulfimide lithiums；The electric conducting lithium salt accounts for the 8.00- of lithium secondary cell electrolyte gross mass 16.00%.
5. lithium secondary cell electrolyte according to claim 1 or 2, which is characterized in that the organic solvent is by cyclic annular molten The mass ratio of agent and linear solvents composition, the cyclic solvent and the linear solvents is (1~2): 3.
6. lithium secondary cell electrolyte according to claim 5, which is characterized in that the cyclic solvent is selected from ethylene carbonate One or more of ester, propene carbonate, fluorinated ethylene carbonate, gamma-butyrolacton and gamma-valerolactone.
7. lithium secondary cell electrolyte according to claim 5, which is characterized in that the linear solvents are selected from carbonic acid diformazan One or more of ester, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propyl carbonate and propyl propionate.
8. a kind of lithium secondary battery, which is characterized in that include the described in any item lithium secondary cell electrolytes of claim 1-7.
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